TWI254192B

TWI254192B - Hydroxyphenyl copolymers and photoresists comprising same

Info

Publication number: TWI254192B
Application number: TW089100385A
Authority: TW
Inventors: Ashish Pandya; Roger F Sinta; Hiroshi Ito
Original assignee: Shipley Co Llc; Ibm
Priority date: 1999-01-12
Filing date: 2000-01-12
Publication date: 2006-05-01
Also published as: KR20000052413A; JP2000284483A; US6770413B1; EP1020768A1; KR100669188B1; JP4695242B2

Abstract

The present invention relates to new copolymers and use of such copolymer as a resin binder component for photoresist compositions, particularly chemically-amplified positive-acting resists. Polymers of the invention include repeat units of (1) meta-hydroxystyrene groups, (2) para-hydroxystyrene groups, and (3) photoacid-labile groups.

Description

1254192 B7 五、發明說明（1 ) [發明背景] [發明領域] 本發明係關於一種新穎共聚物，以及該共聚物作為光阻（特別是化學倍增式正光阻）組成物之樹脂黏合劑成分之用途。本發明之聚合物包含⑴光酸式不穩定基（咖士議仏| labUe groups)、（2)間-羥苯基、以及（3)對羥苯基 [背景] 光阻係使用於轉移影像至基板的感光性薄膜。基板上塗覆-層光阻，該光阻塗層經由活性輕射光源穿透光罩而曝光。此光罩含有活性輻射穿不透之不透光區域，及活性輻射可穿透之透明區域。藉由曝光於活性輻射下，該光阻丨塗層進行光誘導化學轉換，而將光罩圖案轉移到含有塗層之基板上。曝光後，該光阻經顯影提供浮雕影像㈣ief mage)而可對基板做選擇性加工處理一光阻可為正光阻或負光阻。以負光阻而言，受曝在活 ^輻射下之塗層部份，光阻組成物之感光化合物與可聚合 $劑之間會產生聚合或交聯作用，結果，使塗層之曝光部份較未曝光部份難溶於顯影劑溶液中。以正光阻而言，^ 曝光部份成為易溶於顯影劑溶液中，而未曝對顯影劑之難玄栎。加& ^ τ 1 ”呆持肖i之難命。-般而s，光阻組成物包括至少消線樹脂勒合劑成分與一種光活性劑。尤其目别化學倍增式光阻劑已被廣泛利用， =:!像’及其他高性能之應用上。該光阻；」每單位光生性酸（p_ge⑽則acid) 本紙張尺度翻^iiii^(CNS)A4規格（21Q x 297公釐）" 91566 1 1254192 A7 B7 五、發明說明（2 ) (請先閱讀背面之注音？事項再填寫本頁) 一般包含有許多交聯作用（如負光阻）、或去保護性反應（如正光阻）。以化學倍增式正光阻而言，係使用陽離子性光啟動劑，以誘導自光阻黏合劑側出之“封阻，，（“blocking，，) 基進行裂解；或誘導包括光阻黏合劑主架構之一些基團進行裂解。參見例如美國專利5,075，199、4,968,581、 4,883,740、4,810,613 與 4,491，628 等案，及加拿大專利申請案2,001，384。該樹脂之塗覆層經曝光產生封阻基之裂解時，形成極性官能基（如，羧基或醯亞胺）而造成光阻塗覆層曝光部分與未曝光部份有不同之溶解度特性。亦參見R.D· Allen等人發表於1996年SPIE會刊第2724卷中之 334 至 343 頁；及 P· Trefonas 等人（P. Trefonas et al.) 發表於1997年10月6曰第11屆國際光聚合物會議會刊（塑料 JL 程師學會 UProceedings of the IIth International Conference on Photopolymers (Soc, of Plastics Engineers)] 中之44至58頁。目前市面上可用的光阻劑適合應用於許多方面，然而’卻也暴露出明顯的缺失，特別是在例如形成高解析度經濟部智慧財產局員Η消費合作社印製半次微米（sub-half micron)與 1/4 次微米（sub-quarter micron)特徵等之高性能應用上。 [發明概述] 本發明提供新穎的共聚物、及包含光活性成分以及做為樹脂黏合劑成分之共聚物的光阻組成物。本發明之共聚物一般包括至少一種為間-羥苯基衍生物之重覆單元、至少一種為對·羥苯基衍生物衍生之重覆單元、及一種或一 i紙張尺度適用中國國家標準（CNS)A4規格（21G x 297公髮） ---- 2 91566 1254192 A7 五、發明說明（3 ) 種以上之光酸式不穩定基。 (請先閱讀背面之注意事項再填寫本頁) 、，左發現含有|發明樹脂之光阻劑具有能形成高解析度光阻&象之優異性貝。若光阻具有太高之溶解速率，則將月顯降低其解析度’特別是用於印製微米或次微米特徵時。更發現到，若將間-趣基單元加入至含有對_經苯基與酸式不穩定單元之聚合物中，則在含此聚合物的光阻塗覆層内，會明顯有利地影響曝光區與未曝光區之間的溶解度差異性。本發明令特別適當的共聚物，包含由下列化合物經聚合作用所提供之單元：間-羥基乙烯基苯基化合物(如間羥苯乙稀或間·經基甲基苯乙稀）、對-經苯乙稀（如對_ 羥苯乙烯或對-經基α_甲基苯乙烯）及提供光酸式不穩定基之丙烯酸醋。本發明之聚合物亦含有其他單元，如視需要之苯基（例如由苯乙稀化合物之共聚合作用所提供）、氮基（由丙烯腈之共聚合作用所提供）等。經濟部智慧財產局員工消費合作社印製本發明也提供形成浮雕影像之方法，包含形成高解析洋雕顯像例如線條圖案，其每一線條含垂直之側壁，而線條寬度為約0.40微米或更小，或甚至約〇 25微米或更小、。本發明更進一步提供包括基板之製造物件，例如表面上塗覆本發明之光阻劑而顯現浮雕影像之微電子晶圓、液晶顯示器、或其他平面顯示基板等。本文提及之“共聚物，，係指除均聚物外之聚合物因此包括三元共聚物及四元共聚物等。此外，本文所提之“ 經苯基，’或“對-經苯基，，或其他類似術語，係包含除了0 Μ氏張尺度$用中國國家標準（CNS)A4規格（210 X 297公釐1 ------------- 91566 1254192 A7 五、發明說明（4 ) 特定位置之羥基外，可具有苯環取代基之基團。本發明之共聚物中，較佳者為間-羥苯基之對位無羥基取代，更佳者為在其間位上只由單一羥基取代。本發明之共聚物中， (請先閱讀背面之注意事項再填寫本頁) 較佳者為對-羥苯基之間位無羥基取代，更佳者為在其對位上僅由單一羥基取代。本發明之其他方面如下所述。 [發明之詳細說明] 如上述討論，本發明較佳之共聚物包含至少三種不同的重覆單70 :含酸式不穩定基之單元;含間-羥苯基（例如由間_羥苯乙烯或間_羥基α _甲基苯乙烯之縮合作用所提供）之單元2);及含對-羥苯基（例如由對_羥苯乙烯或對_ 羥基α -甲基苯乙烯之縮合作用所提供）之單元3)。聚合物適需要也可包含其他基團4)。共聚物單元1)為酸式不穩定基。當含該聚合物之光阻塗覆層經曝光下，該共聚物單位將進行光酸式誘導裂解 (photoacid-induced cleavage)而使塗覆層之曝光區與未曝經濟部智慧財產局員工消費合作社印製區產生溶解度差異。本文所指之酸式不穩定基或光酸式不穩定基係依據此等基於其技藝中所認知之意義，係指其具有光酸式誘導裂解能力，以於含有酸式不穩定單元聚合物之光阻塗覆層之曝光區與未曝光區之間提供溶解度差異。酸式不穩定基1)較佳為附著自聚合物主架構側出，一般以丙烯酸酯基較適合，其可由一種或多種經取代或未經取代之烧基丙烯酸酯（例如丙烯酸第三丁酯與甲基丙稀酸第三丁酯）之單體經加成聚合作用或其他反應而形成。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 4 91566 1254192 A7 五、發明說明（5 ) 該適合的單體可由市面上睡 , 面上購侍，或可由已知之化學製程製。該經縮合之丙烯酸酉旨單之側出之經取代醋部份 (請先閱讀背面之注咅？事項再填寫本頁) ㈣，係作㈣出之酸式*穩定基。也可使用其他丙稀酸醋單元；包含具有環狀或非環狀烧基之醋基（上述R基）者，該烷基含有i至約14個碳原子，或一般為含 1至約8個碳原子。另外也可使用含有1個或更多個取代3 基之烷醋基，取代基之例如…，特別是氟、氣或溴；烷氧基；芳基如苯基等。可縮合以提供本發明聚合物丙烯酸酯單元之化合物實例包含丙烯酸丁酯（包含丙烯酸第二丁酯）、甲基丙烯酸丁酯（包含甲基丙烯酸第三丁酯）經濟部智慧財產局員工消費合作社印製等。適合的丙烯酸酯酸式不穩定基中亦包括具下式者： R3〇(c=o)r2ric_，其中R1及R2各自分別選自如氫經取代或未經取代之C1-1G烷基、或拉電子基如鹵原子；及R3 為經取代或未經取代之Cl i4烷基、經取代或未經取代之芳基如苯基、或經取代或未經取代之芳烷基如苯甲基。該經取代基團之取代基可為鹵原子、C16燒基、C16烧氧基、苯基或其他芳基等。醋酸酯基亦可提供如上述之丙烯酸酯基’亦即，藉由一種或多種經取代或未經取代之醋酸乙烯醋類如醋酸丙烯酯等之單體之自由基反應、或其他反應。其他適合之酸式不穩定基包含揭示於美國專利 5,3 62,600，4,968,5 8卜 4,883,74 0，4,810,613，及 4,491，628 等案中者。本發明之共聚物亦包括間-羥苯基2)，及對-羥苯基 3)。該等基團係藉由對應之單體，如視需要經取代之間· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 5 91566 1254192 A7 五、發明說明（6 (請先閱讀背面之注意事項再填寫本頁) 經笨乙稀、間-羥基甲基苯乙烯、對_經基苯乙烯、或對-羥基α-甲基苯乙烯之聚合作用而提供。通常較佳之間羥苯基2)及對-羥苯基3)僅含有單一羥基取代，及由非_童基未取代、或由除反應性基（如光酸式不穩定基）或如羧基等酸性基以外之基團視需要而取代。^，適合的視需垄之非-反應性及非-酸性環取代基包括齒原子、C!—烷氧基、 Cl6燒基等。本文中該“非·反應性基，’係指此基團不會與在含該聚合物之光阻之典型微影加工（曝光前、曝光、曝光後烘烤及顯影步驟）下之酸或熱（通常低於約17〇。〇反應。如上所述，本發明之共聚物除上述之1)、2)及3)單元外，可視需要包括其他單元。例如，本發明之共聚物可含有不含反應性基（如光酸式不穩定基）或如羥基（如存在於酚基中者）、羧基等酸性基之單元4)。根據上述，本文中“不含反基”之此等附加單元4)係指此基團不會與在含該共聚物之光阻之典型微影加工（前_曝光、曝光、曝光後烘烤及顯影步驟）下之酸或熱（通常低於約17〇。〇反應。經濟部智慧財產局員工消費合作社印製特佳之附加單元4)為視需要經取代之苯基，並可由視的要經取代之苯乙締反應來提供，其中該視需要取代基係包3如鹵原子、貌氧基、院基等環取代基之非-反應性基。其他較佳之共聚物單元4)包括具有高碳含量，如一單元總質量之至少約75%為碳者，更佳為一單元總質量之至少約80% ’或甚至至少9〇%以上為碳者。除視需要 H代^苯基外，特佳1之基包含經取代及未經取代之芳本紙張尺度適财關家規格⑵Q χ挪公愛） 6 91566 A7 1254192 五、發明說明（7 ) 基，如含約6到18個芳族碳之基，例如由伸萘基、伸苊基等縮合所提供之基’以及視需要經取代之乙烯基脂環基包含具有5至約12個碳原子者，例如經取代或未經取代之乙烯基去甲萡烷基、乙烯基金剛烷基或乙烯基環己烷。也可使用如含1至約12個碳原子之非環狀視需要經取代之烷基，但通常以芳基或脂環基較為適合。視需要經取代基之較佳取代基包含如q·8烷氧基，特別是甲氧基、乙氧基、丙氧基、氰基、鹵原子（氟、氣、溴或碘卜含2至约10個碳原子之炔基、含1至約10個碳原子之烷硫基等。如上所述，這些附加之視需要單元，最好不含酸性取代基 (如羥基、羧基等）或光酸式不穩定取代基（如酸性不穩定酯）。本發明較佳之共聚物包括含下式I之結構者： ΓΜ先閱讀背面之注意事項再填寫本頁)1254192 B7 V. OBJECTS OF THE INVENTION (1) [Background of the Invention] [Technical Field] The present invention relates to a novel copolymer, and the copolymer as a resin binder component of a photoresist (particularly a chemically multiplying positive photoresist) composition use. The polymer of the present invention comprises (1) photoacid-labile groups (labUe groups), (2) m-hydroxyphenyl group, and (3) p-hydroxyphenyl [background] photoresist system for transfer imaging. A photosensitive film to the substrate. A layer-to-layer photoresist is applied over the substrate, and the photoresist coating is exposed through an active light source through the reticle. The reticle contains an opaque region through which the active radiation is impermeable and a transparent region through which the active radiation can penetrate. The photoresist layer is photoinduced chemically converted by exposure to active radiation, and the mask pattern is transferred to a substrate containing the coating. After exposure, the photoresist is developed to provide a relief image (4) and can be selectively processed on the substrate. The photoresist can be positive or negative. In the case of negative photoresist, the coating portion exposed to the active radiation, polymerization or cross-linking between the photosensitive compound of the photoresist composition and the polymerizable agent, results in the exposure portion of the coating. The portion is less soluble in the developer solution than the unexposed portion. In terms of positive photoresist, the exposed portion becomes soluble in the developer solution without being exposed to the developer. Adding & ^ τ 1 ” is difficult to hold. In general, the photoresist composition includes at least a wire-removing resin component and a photoactive agent. In particular, chemical multiplying photoresists have been widely used. Utilize, =:! like 'and other high performance applications. The photoresist; ” per unit photoacid (p_ge(10) acid) This paper scale turns ^iiii^(CNS)A4 specification (21Q x 297 mm)&quot 91566 1 1254192 A7 B7 V. INSTRUCTIONS (2) (Please read the phonetic on the back? Please fill out this page) Generally, there are many cross-linking effects (such as negative photoresist) or de-protective reactions (such as positive photoresist). ). In the case of chemically multiplying positive photoresists, cationic photoinitiators are used to induce "blocking," (blocking,) radicals from the side of the photoresist, or to induce photoresists including photoresists. Some groups of the structure are cleaved. See, for example, U.S. Patent Nos. 5,075,199, 4,968,581, 4, 883, 740, 4, 810, 613, and 4, 491, 628, and the Canadian Patent Application No. 2, 001, 384. When the coating layer of the resin is subjected to exposure to form a blocking group, a polar functional group (e.g., a carboxyl group or a quinone imine) is formed to cause a difference in solubility characteristics between the exposed portion of the photoresist coating layer and the unexposed portion. See also 334-343 of RD Allen et al., published in the 1996 issue of the SPIE journal, Volume 2724; and P. Trefonas et al. (P. Trefonas et al.), published on October 6, 1997, 11th International 44-58 of the UProceedings of the IIth International Conference on Photopolymers (Soc, of Plastics Engineers). Currently available photoresists are suitable for many applications, however 'But it also reveals obvious defects, especially in the formation of sub-half micron and sub-quarter micron features, such as the formation of high-resolution economic ministry intellectual property bureaus and consumer cooperatives. SUMMARY OF THE INVENTION [Technical Summary] The present invention provides a novel copolymer, and a photoresist composition comprising a photoactive component and a copolymer as a resin binder component. The copolymer of the present invention generally comprises at least one a repeating unit of a hydroxyphenyl derivative, at least one repeating unit derived from a p-hydroxyphenyl derivative, and one or one i-paper scale applicable to the China National Standard (CNS) A4 gauge (21G x 297 mil) ---- 2 91566 1254192 A7 V. Description of invention (3) More than one kind of photoacid unstable group (Please read the note on the back and fill in this page) The photoresist of the invention resin has the superiority of being able to form a high-resolution photoresist & image. If the photoresist has a dissolution rate that is too high, the resolution is lowered by the moon', especially for printing micron or In the case of submicron features, it has been found that if a meta-family unit is added to a polymer containing a p-phenyl group and an acid-labile unit, then in the photoresist coating layer containing the polymer, It is clearly advantageous to influence the solubility difference between the exposed and unexposed regions. The present invention makes a particularly suitable copolymer comprising a unit provided by polymerization of the following compounds: a meta-hydroxyvinylphenyl compound (e.g., meta-hydroxyl) Acetylene or m-vinyl styrene), p-benzoic acid (such as p-hydroxystyrene or p-cyano α-methylstyrene) and acrylic acid providing photoacid-labile groups Vinegar. The polymer of the invention also contains other units, as needed a base (for example, provided by copolymerization of a styrene compound), a nitrogen group (provided by copolymerization of acrylonitrile), etc. Printing by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumption Cooperative, The present invention also provides a method of forming a relief image Including forming a high resolution oceanographic image such as a line pattern, each of which has vertical sidewalls, and the line width is about 0.40 microns or less, or even about 25 microns or less. The present invention still further provides articles of manufacture including substrates, such as microelectronic wafers, liquid crystal displays, or other flat display substrates, on which a photoresist of the present invention is applied to a surface to exhibit relief images. As used herein, "copolymer" means a polymer other than a homopolymer and thus includes terpolymers and tetrapolymers, etc. Further, as referred to herein, "p-phenyl," or "p-benzoic acid" Base, or other similar terms, are included in addition to 0 Μ Zhang scales $ with Chinese National Standard (CNS) A4 specifications (210 X 297 mm 1 ------------- 91566 1254192 A7 five (4) A group having a benzene ring substituent in addition to a hydroxyl group at a specific position. Among the copolymers of the present invention, preferably, the para-hydroxyphenyl group has no hydroxyl group substitution, and more preferably In the interstitial position, it is only substituted by a single hydroxyl group. In the copolymer of the present invention, (please read the note on the back side and then fill in the page). Preferably, the p-hydroxyphenyl group has no hydroxyl group substitution, and more preferably It is substituted by a single hydroxyl group in the para position. Other aspects of the invention are as follows. [Detailed Description of the Invention] As discussed above, preferred copolymers of the invention comprise at least three different repeating sheets 70: acid-containing instability Unit of a base; containing a meta-hydroxyphenyl group (for example, from m-hydroxystyrene or m-hydroxy alpha-methylstyrene) Unit 2) provided by condensation; and unit 3) containing p-hydroxyphenyl group (for example, provided by condensation of p-hydroxystyrene or p-hydroxyl-methylstyrene). Other groups 4) may also be included. The copolymer unit 1) is an acid labile group. When the photoresist coating layer containing the polymer is exposed, the copolymer unit will undergo photoacid-induced cleavage (photoacid- Induced cleavage), the exposed area of the coating layer and the unexposed economic department intellectual property bureau employee consumption cooperative printing area produce solubility difference. The acid unstable group or photoacid unstable base referred to herein is based on The meaning recognized in the art refers to its photoacid-induced cleavage ability to provide a solubility difference between the exposed and unexposed regions of the photoresist coating containing the acid-labile unit polymer. The labile group 1) is preferably attached to the side of the polymer backbone, and is generally suitable for acrylate groups, which may be substituted by one or more substituted or unsubstituted alkyl acrylates (eg, tert-butyl acrylate and alpha) Third acrylic acid The monomer of the ester is formed by addition polymerization or other reaction. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 4 91566 1254192 A7 V. Invention description (5) The suitable single The body can be slept on the market, purchased on the surface, or can be made by a known chemical process. The condensed acrylic enamel is used to replace the vinegar portion (please read the back of the note? (d), is the (4) acid type * stabilizing group. Other acrylic acid vinegar units can also be used; including carboxylic acid groups having a cyclic or acyclic alkyl group (the above R group), the alkyl group contains i to About 14 carbon atoms, or generally from 1 to about 8 carbon atoms. Further, an alkyl acrylate group having one or more substituted 3 groups, a substituent such as ..., particularly fluorine, gas or bromine; an alkoxy group; an aryl group such as a phenyl group or the like can also be used. Examples of compounds which can be condensed to provide the polymer acrylate unit of the present invention include butyl acrylate (containing a second butyl acrylate), butyl methacrylate (including a third butyl methacrylate) Ministry of Economics Intellectual Property Office Staff Consumer Cooperative Printing and so on. Also suitable for the acrylate acid-labile group are those having the formula: R3〇(c=o)r2ric_, wherein R1 and R2 are each independently selected from a C1-1G alkyl group such as hydrogen substituted or unsubstituted, or An electron group such as a halogen atom; and R3 is a substituted or unsubstituted Cl i4 alkyl group, a substituted or unsubstituted aryl group such as a phenyl group, or a substituted or unsubstituted aralkyl group such as a benzyl group. The substituent of the substituted group may be a halogen atom, a C16 alkyl group, a C16 alkoxy group, a phenyl group or another aryl group or the like. The acetate group may also provide a radical reaction such as the above-mentioned acrylate group, i.e., a monomer such as one or more substituted or unsubstituted vinyl acetate vinegars such as propylene acetate, or the like. Other suitable acid labile groups are disclosed in U.S. Patent Nos. 5,3,62,600, 4,968, 5, 8, 4, 883, 7, 0, 4, 810, 613, and 4, 491, 628 et al. The copolymer of the present invention also includes m-hydroxyphenyl 2), and p-hydroxyphenyl 3). These groups are made by the corresponding monomers, if required, if necessary. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 5 91566 1254192 A7 V. Description of invention (6 ( Please read the precautions on the back and fill out this page.) Provided by the polymerization of stupid ethylene, m-hydroxymethylstyrene, p-hydroxystyrene, or p-hydroxy α-methylstyrene. Between hydroxyphenyl 2) and p-hydroxyphenyl 3) contains only a single hydroxy substitution, and is unsubstituted by a non-phenyl group, or is acidated by a reactive group (such as a photoacid-labile group) or a carboxyl group. Subgroups other than the base are substituted as needed. ^, Suitable non-reactive and non-acidic ring substituents of the desired ridge include a tooth atom, a C!-alkoxy group, a Cl6 alkyl group, and the like. As used herein, "non-reactive group," means that the group does not react with the typical lithography process (pre-exposure, exposure, post-exposure bake and development steps) of the photoresist containing the polymer or Heat (usually less than about 17 Torr. 〇Reaction. As noted above, the copolymer of the present invention may include other units as desired, in addition to units 1), 2) and 3) above. For example, the copolymer of the present invention may contain a unit which does not contain a reactive group (such as a photoacid-labile group) or an acidic group such as a hydroxyl group (such as those present in a phenol group), a carboxyl group, etc. 4). According to the above, "there is no anti-group" herein. The additional unit 4) means that the group does not react with acid or heat (usually less than about) under typical lithographic processing (pre-exposure, exposure, post-exposure bake and development steps) of the photoresist containing the copolymer. 17〇.〇 Reaction. The Ministry of Economic Intelligence's Intellectual Property Bureau employee consumption cooperative prints a special additional unit 4) phenyl which is replaced as needed, and can be provided by a benzene-ethylation reaction to be replaced, as needed Substituent group 3 such as a halogen atom, amorphous oxy group, and a hospital base Non-reactive groups of ring substituents. Other preferred copolymer units 4) include those having a high carbon content, such as at least about 75% of the total mass of a unit being carbon, more preferably at least about 80% of the total mass of a unit. Or even at least 9% or more of the carbon. Except for the need of H, phenyl, the base of the special 1 contains the substituted and unsubstituted plaid paper size specifications (2) Q χ 公公 ) 6 91566 A7 1254192 V. INSTRUCTION DESCRIPTION (7) A group, such as a group containing from about 6 to 18 aromatic carbons, such as a group provided by condensation of an anthranyl group, a fluorenyl group, and the like, and optionally substituted vinyl alicyclic groups Included having from 5 to about 12 carbon atoms, such as substituted or unsubstituted vinyl normethane, vinyl adamantyl or vinyl cyclohexane. It may also be used, for example, from 1 to about 12 carbons. The atom of the atom is optionally substituted with an alkyl group, but is usually preferably an aryl group or an alicyclic group. Preferred substituents of the substituent include, for example, a q.8 alkoxy group, particularly a methoxy group. Ethoxy, propoxy, cyano, halogen atom (fluorine, gas, bromine or iodine containing 2 to about 10 carbons An alkynyl group of an atom, an alkylthio group having 1 to about 10 carbon atoms, etc. As described above, these additional optional units preferably do not contain an acidic substituent (e.g., a hydroxyl group, a carboxyl group, etc.) or a photoacid instability. Substituents (e.g., acid labile esters). Preferred copolymers of the present invention include those having the structure of formula I: ΓΜRead the back of the first note and fill out this page)

經濟部智慧財產局員工消費合作社印製其中W為包括光酸式不穩基之單元； R1及R2各自為相同或不同之非-氫取代基； R、R及R5各自分別為氫原子 '或視需要經取代之烷基； m及η各自分別為〇(當每個可用之苯環位置已由氫所取代）至4 ;Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, where W is a unit containing photoacid-labile groups; R1 and R2 are each the same or different non-hydrogen substituents; R, R and R5 are each a hydrogen atom' or An alkyl group which is optionally substituted; m and η are each 〇 (when each available benzene ring position has been replaced by hydrogen) to 4;

91566 1254192 A7 五、發明說明（8 ) " " -- x、y及z各自大於0，且為以聚合物聚合物單元之莫耳分率或百分率。、、兀计之各別如上所述，較佳之光酸式不穩定丨”姐说4人nr ττ 土 W為丙烯酸酯基，以k供包含下式II結構之聚合91566 1254192 A7 V. INSTRUCTIONS (8) "" -- x, y and z are each greater than 0 and are in mole fraction or percentage of polymer polymer units. As described above, the preferred photoacid-acidic instability 丨" said that 4 people nr ττ soil W is an acrylate group, and k is used for the polymerization of the structure of the following formula II.

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II 其中R為視需要經取代之烷基’ 双住為含約4個至約12個碳原子；更典型者為含約4 ㈣主約6個碳原子，並具有分支之非環狀基如第三丁基月曰環基如金剛烧基四氫吡喃基及去甲萡烷基； W、X及y各自大於〇,且為以聚合物總單元計之各別聚合物單元的莫耳分率或百分率，·以及 R、R2、R3、R4、r5、m、n 各自鱼分目與上式I之定義相同。經濟部智慧財產局員工消費合作社印製如前所述，本發明較佳之聚合物亦包括含有附加之3 覆單元者’特別是不含酸性基[如’羥基（如存在紛基中者）、叛基]或不含酸性反應基（如光酸性不穩定部份）之基。更詳言之’本發明較佳之聚合物包括含下sni之結構1 Μ氏張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 8 91566 1254192 A7 B7 五、發明說明（9II wherein R is an optionally substituted alkyl 'double live containing from about 4 to about 12 carbon atoms; more typically about 4 (four) main about 6 carbon atoms, and having a branched acyclic group such as a third butyl fluorenyl ring group such as an adamantyl tetrahydropyranyl group and a nortenyl group; each of W, X and y is larger than fluorene, and is a molar of individual polymer units in terms of total polymer units. The fraction or percentage, · and R, R2, R3, R4, r5, m, n are the same as the definition of the above formula I. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives, as mentioned above, the preferred polymers of the present invention also include those containing additional 3 units, especially those that do not contain acidic groups [such as 'hydroxy groups (if any) Rebel base or a base that does not contain an acidic reactive group (such as a photoacid labile moiety). More specifically, the preferred polymer of the present invention comprises a structure comprising a lower sni. The scale of the sni is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 8 91566 1254192 A7 B7 5. Invention Description (9

III 其中W、R1、R2、R3、R4、R5、m及n各自與上式I 之定義相同，R6與式I之R3、R4、及R5之定義相同； S為不含酸性或反應性部份之基，· w’、X’、y’及ζ’大於0，且為以聚合物總單元計之各別聚合物單元的莫耳分率或百分率。本發明特別較佳的共聚物包含下式IV之結構：III wherein W, R1, R2, R3, R4, R5, m and n are each the same as defined in the above formula I, and R6 has the same definition as R3, R4 and R5 of the formula I; S is an acid-free or reactive moiety The base, w', X', y' and ζ' are greater than 0 and are the molar fraction or percentage of the individual polymer units in terms of the total polymer units. Particularly preferred copolymers of the invention comprise a structure of the following formula IV:

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IV 經濟部智慧財產局員工消費合作社印製其中R為視需要經取代之烷基，該烷基以含4至約1 8 個碳原子為適當，較佳為分支鏈之非環狀基如第三丁基，或為脂環基如金剛烷基、四氫吡喃基、或去甲宿烷基； R1’，R2’及R3’各自分別為氫或甲基； w、X及y各自大於〇，且為以聚合物總單元計之各別聚合物單元的莫耳分率或百分率。以W、Χ及y之總和為至少約70%較佳，更佳為至少約80、85、90或95%，又更佳為w、X及y之總和為ι〇〇〇/0。上式I及III中適當的W基很廣泛，包含上述單元。紙張尺度it用中國國家標準（CNS)A4規格（21G X 297公釐） 91566 9 1254192 經濟部智慧財產局員工消費合作社印製 10 A7 --_B7 --~------- 五、發明說明（10 ) 中之酸式不穩定基。式II中較佳之R其炎又住4 K i為視需要經取代之烷基，該烷基較佳含有約4個至約10個碳原子；更典型者為含約4個至約8個碳原子。分支鏈烷基如第三丁美，為一般之較佳R基。藉由於聚合物合成時使用不同之^ 烯酯單體，該聚合物亦可包括不同w或R基之混合物。 ^上式I至ΠΙ之典型R1及R2基包含如*原子（特別為氟、氣、或溴）、Ch烷基、Cl_8烷氧基、c28烯基、烯基或炔基、芳基如苯基、烷醯基如C16烷醯基（如乙酿8 基）等。R1及R2基一般較不宜為酸性基或反應性基，如翔基、羧基、-COOH或其他可與光酸類（如酯類）反應之基。式I至IV中任一式之R3，r4，R5及r6 一般為4 烷基或氫，更典型為甲基或氫。式III共聚物中適當之s基包含芳基如苯基、萘基或類似基，脂環基或金剛烷基、去甲萡烷基或類似基。〜I 而言，上述視需要之單元4)之基為適當之單元S。视需要被非反應性基（如鹵原子、烷氧基、烷基等）取代之笨基為一般較佳之S基。此苯基S基可由苯乙烯單元反應而提供。該S基可適當地以聚合物總單元之約1至約5 〇莫耳百分率，更典型地以聚合物總單元之約3至約30莫耳百分率，又更典型地以聚合物總單位之約5至約20或約25 莫耳百分率之量存在。上述之視需要經取代之基（包含R、R1、R2、R3、R4、 R5及R6)可在一個或更多個可用位置上由一個或更多個適當基取代，其中取代基如鹵原子（特別是氟、氣、或濞）、本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 91566 ----------------- 訂 I ^--------線 (請先閱讀背面之注音？事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製 1254192 五、發明說明（11IV Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, which prints R as an alkyl group which is optionally substituted. The alkyl group is suitably from 4 to about 18 carbon atoms, preferably a branched chain such as a Tributyl, or an alicyclic group such as adamantyl, tetrahydropyranyl, or desyloxy; R1', R2' and R3' are each hydrogen or methyl; w, X and y are each greater than 〇, and is the molar fraction or percentage of the individual polymer units in terms of the total polymer units. Preferably, the sum of W, Χ and y is at least about 70%, more preferably at least about 80, 85, 90 or 95%, and even more preferably the sum of w, X and y is ι〇〇〇/0. Suitable W groups in the above formulae I and III are broad and comprise the above units. Paper scale is used in China National Standard (CNS) A4 specification (21G X 297 mm) 91566 9 1254192 Printed by the Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative 10 A7 --_B7 --~------- V. Invention Describe the acid labile group in (10). Preferably, R in the formula II has 4 K i as an optionally substituted alkyl group, and the alkyl group preferably contains from about 4 to about 10 carbon atoms; more typically from about 4 to about 8 carbon atom. Branched chain alkyl groups such as tert-butyl are generally preferred R groups. The polymer may also comprise a mixture of different w or R groups by the use of different ethylenic ester monomers for polymer synthesis. The typical R1 and R2 groups of the above formula I to 包含 include, for example, * atoms (especially fluorine, gas, or bromine), Ch alkyl, Cl-8 alkoxy, c28 alkenyl, alkenyl or alkynyl, aryl such as benzene Alkyl group, such as a C16 alkano group (such as a ethoxylate 8 group). The R1 and R2 groups are generally less preferred to be acidic or reactive groups such as sulfhydryl, carboxyl, -COOH or other groups which are reactive with photoacids such as esters. R3, r4, R5 and r6 of any of formulae I to IV are generally 4 alkyl or hydrogen, more typically methyl or hydrogen. Suitable s groups in the copolymer of formula III comprise an aryl group such as phenyl, naphthyl or the like, an alicyclic group or an adamantyl group, a nortenyl group or the like. For the case of I, the above-mentioned unit 4) is the appropriate unit S. The stupid group which is optionally substituted with a non-reactive group (e.g., a halogen atom, an alkoxy group, an alkyl group, etc.) is a generally preferred S group. This phenyl S group can be provided by reaction of a styrene unit. The S group may suitably be from about 1 to about 5 mole percent of the total polymer unit, more typically from about 3 to about 30 mole percent of the total polymer unit, and more typically in total polymer units. An amount of from about 5 to about 20 or about 25 mole percent is present. The above-mentioned substituted group (including R, R1, R2, R3, R4, R5 and R6) may be substituted by one or more suitable groups at one or more available positions, wherein the substituent is a halogen atom. (especially fluorine, gas, or helium), this paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 91566 ----------------- ^--------Line (please read the phonetic transcription on the back? Please fill out this page again) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1254192 V. Invention description (11

Cm烧基、Cl_8烧氧基、CM烯基、& 8烯基或炔基、芳族羥基如苯基、烷醯基如Cw烷醯基（如乙醯基）等。典型之經取代部分為在1個、2個或3個可用你里u 叫』用位置上經取代者。上式卜n、m、及lvt，特定莫耳分率或百分率可適當地於相當寬廣範圍内有所不同。例如，各式中之X、 W及W’（酸性不穩定基之莫耳百分率）可刀平）可適當地為共聚物總單元之i至約90莫耳百分率，更典型為共聚物總單元之約5至約80莫耳百分率；間-羥苯基單元之莫耳百分率（式 I中之y，其他式中之X及X，）與對-羥苯基單元之莫耳百$ 分率(式I中之z，其他式中之y或y，)各適當地為共聚物總單元之約5或10至約50莫耳百分率，更典型為共聚物總單元之15或20至約40莫耳百分率；及式Ιπ中z,可為共聚物總單元之約1至約70或80莫耳百分率，更典型為共聚物總單元之約5或10莫耳百分率至約3〇、4〇、5〇或60莫耳百分率。通常在共聚物中以間-羥苯基單元比對 -羥苯基單元存在更多之莫耳量為較佳。本發明特佳者為’上式I至式IV特定單元之莫耳百分率為如下所述：酸性不穩定單元（式J中之甘丄 1、x，其他式中之w或W’）為共聚物總單元之約3至約50莫耳百八率更佳為共聚物總單元之約4至約3 0莫耳百分率、又t ^圭為約5至約25莫耳百分率’甚更佳為共聚物總單元之約 8至約20莫耳百分率；間-羥苯基單元（式I中 T i y，其他式中之X或X’）為共聚物總單元之約40至約ν 、吴耳百分率，更佳為約50至約85莫耳百分率，又更祛去劣Α 八又住耆為共聚物本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 91566 -------------------訂·--------線 (請先閱讀背面之注意事項再填寫本頁) 11 1254192 經濟部智慧財產局員工消費合作社印製 12 A7 五、發明說明（U ) 總單元之約60至約70或姑〆莫耳百分率；對_經苯基單元 (式I中之z;其他式中之杰 < y或y )為共聚物總單元之約5 至約40莫耳百分率，更佳氣更佳為約8至約35莫耳百分又更佳為共聚物總單元之約】n s ^ W至約20或25莫耳百分率。通常較佳為以上式I、ττ 飞丄π、ΠΙ及IV中描述之基構成聚合物之主要部份。詳今之， ° 式Ϊ中較佳為x、y&z之總和為聚合物總單元之至φ v約60莫耳百分率，更佳為至少約70或80百分率，又更隹Cm alkyl group, Cl_8 alkoxy group, CM alkenyl group, & 8 alkenyl or alkynyl group, aromatic hydroxy group such as phenyl group, alkyl fluorenyl group such as Cw alkanoyl group (e.g., ethenyl group) and the like. A typical substituted part is one that is replaced by one, two, or three available positions. In the above formula, n, m, and lvt, the specific molar fraction or percentage may suitably vary within a relatively wide range. For example, X, W and W' (percentage of molarity of the acid labile group) in the formulas may suitably be from i to about 90 mole percent of the total unit of the copolymer, more typically the total unit of the copolymer. From about 5 to about 80 mole percent; the molar percentage of m-hydroxyphenyl units (y in formula I, X and X in the other formula) and the molar percentage of p-hydroxyphenyl units (z in formula I, y or y in the other formula, each) suitably from about 5 or 10 to about 50 mole percent of the total units of the copolymer, more typically from 15 or 20 to about 40 of the total unit of copolymer The percentage of moles; and z in the formula π, may be from about 1 to about 70 or 80 mole percent of the total unit of the copolymer, more typically from about 5 or 10 mole percent of the total copolymer unit to about 3 Torr, 4 Torr. , 5〇 or 60 mole percentage. It is generally preferred that more mole is present in the copolymer as a meta-hydroxyphenyl unit than a p-hydroxyphenyl unit. The molar percentage of the specific unit of the above formula I to formula IV is as follows: an acid labile unit (glycan 1, x in the formula J, w or W' in the other formula) is copolymerized Preferably, the total unit has a ratio of from about 3 to about 50 moles, preferably from about 4 to about 30 mole percent of the total copolymer unit, and from about 4 to about 25 mole percent, even more preferably The copolymer total unit is from about 8 to about 20 mole percent; the meta-hydroxyphenyl unit (T iy in formula I, X or X' in the other formula) is from about 40 to about ν of the total unit of the copolymer, The percentage, more preferably from about 50 to about 85 moles, is even worse. Eighty live and use it as a copolymer. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 91566 --- ----------------Settings--------Line (please read the notes on the back and fill out this page) 11 1254192 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperative Printed 12 A7 V. Inventive Note (U) Approximately 60 to about 70 of the total unit or a percentage of the molar percentage; a pair of phenyl units (z in formula I; other formulas in < y or y) Copolymer unit 5 to about 40 mole percent, more preferably the gas is more preferably from about 8 to about 35 mole percent and more preferably from about n s ^ W] to about 20 or 25 mole percent of total units of the copolymer. It is generally preferred that the groups described in the above formula I, ττ, 丄, ΠΙ, and IV constitute a major part of the polymer. More specifically, the sum of x, y & z is preferably about 60 mole percent of the total polymer unit to φ v , more preferably at least about 70 or 80 percent, and more

佳為w、X及y之總和為共聚物總単元之至少約90或95曾K 莫耳百分率。許多情形下，以聚合物只含有所述之酸性尤孩心暇性不穩定單元及間_及對·羥元為特佳，即式I中x、v及7 + 本I早 y及z之總和等於1〇〇〇/0。同樣地，式III中以W，、X，、y，及7,夕祕像也之總和為共聚物總單元之至少約60%為較佳，更佳為至夕約70或80%，又更佳為w，、 X’、y’及Z’之總和為聚合物嬙物…早兀之至少約90或95莫耳百分率。許多情形下，*主、特佳為式Ιπ之共聚物只包含所述之酸性不穩定基、間-及對_鉍婪1 ^ ^ 了 I本基早疋’及非酸性/非反應性基s為較佳，即式m中w，、X，、丫，及ζ，之總和等於約⑽％者。同樣地，式IIAIV各式中，較佳為wx及 y之總和為聚合物總單元之至少約6〇莫耳百分率，更佳為至少約70或80%，又f私焱 Λ ^ 入更仏為w、X及y之總和為聚合物總單元之至少9“戈95莫耳百分率。許多情形下，特別佳為聚合物只含有所述之酸性不穩定單元及間及對-經苯基單元’即式II及IV各式中之w、u y之總和等於1〇〇%。月之聚合物可於自由基引發劑存在下，在惰性氛 ‘紙張尺度適时國國家標準（CNS)A4規袼（21G x 297公 91566 --------------------r 訂 _ “--------線 (請先閱讀背面之注咅？事項再填寫本頁} 1254192 A7 五、發明說明（I3 ) (請先閱讀背面之注意事項再填寫本頁) 圍（如N2或氬氣）及例如約70它或7〇以上之高溫下，藉由例如自由基聚合反應，或如眾多單體之反應以提供如上述之各種單元予以製備；其中反應溫度可隨所使用特定試劑之反應性及反應溶劑（如使用溶劑）之沸點而有所不同；可參考下文實施例I之示範反應條件。任一定別系統之適當反應溫度可由習知此項技術者依據本發明所揭示内容依經驗決定之。反應溶劑可視需要使用之。適當之溶劑包含醇，如丙醇及丁醇；及芳族溶劑，如苯、氣苯、甲苯及二甲苯。二甲亞楓及二甲基甲醯胺也適用。聚合化反應可不使用反應溶劑而進行。可使用多種自由基起始劑製備本發明之共聚物。例如’可使用偶氮化合物如偶氮-雙_2,2，_異丁腈（AIBN)及偶氮·雙（環己腈），也可使用過氧化物、過酸酯、過酸及過硫酸鹽。經濟部智慧財產局員工消費合作社印製含羥基（如間-羥苯乙烯或對-羥苯乙烯）或其他反應性部份之單體，可視需要縮合成“掩蔽，，（“masked”）形式以利聚合物之合成。例如間-醋酸基苯乙烯及對-醋酸基苯乙烯可分別被使用成為間-羥苯乙烯及對-羥苯乙烯之‘‘掩蔽”形式。其他羥基掩蔽劑或保護基，如烷基甲矽烷基（與經基部份形成矽烷基醚），例如（CH3)3Si-，（CH3)2(丁基）Si-’（（CH3)3C)3Si-等；或其他烷基酯如 CH3CH2(C = 〇> 等也適當。待反應完成後，可在驗性條件下移除此掩蔽基。例如，在如ΝΗ,ΟΗ或NIOAC之鹼存在下，可加熱形成本紙張尺度適用中國國家標準（CNS)A4規格⑽x 297公着） 13 91566 1254192 A7 B7 五、發明說明（Η ) 的聚合物。可參考實施例〗之示範條件。 (請先閱讀背面之注意事項再填寫本頁) 該單體亦可適當地直接，亦即呈“未掩蔽，，形式，予以反應，例如，藉由間_羥苯乙烯、對-羥苯乙烯、及含光酸性不穩定定基之單體如丙烯酸第三丁酯、甲基丙烯酸第三丁酯等之聚合作用。本發明一般較佳之共聚物，其平均分子量（Mw)為 1，000至約1〇〇,〇〇〇，更佳為約2，_至約3〇〇〇〇 ;甚更佳者分子量為約5,〇〇〇或8,000至約25,000或30,000 ;其適當之分子量分布（Mw/Mn)為約3或小於3，較佳為約2或小於2。本發明聚合物之分子量（Mw或Mn)可由凝膠滲透色4法測定之。本發明共聚物適當之分子量分布包含約i 至5，更典型者為約丨至3或4。已發現在水性氫氧化四甲基銨溶液中之溶解速率隨本發明共聚物分子量增加而減低。如上述，本發明之共聚物可非常有用地作為光阻組成物，特別是化學倍增式正光阻之樹脂黏合劑成分。本發明經濟部智慧財產局員工消費合作社印製之光阻劑一般包括光活性成分，及含有上述共聚物之樹脂黏合劑成分。該樹脂黏合劑成分之用量應足以使光阻塗覆層與水性鹼性顯影劑顯影。本發明之光阻組成物亦包括光酸釋出劑（即“ pAG”），其用量應適當而足以於曝光在活性輻射時於光阻塗覆層上產生潛在影像。本發明光阻中所用之一組較佳之pAG，包含例如下泰紙張尺度適用中國國家標準（CNS)A4規格（21“ 297公釐）· 14 91566 1254192 A7 五、發明說明（U ) 式化合物之亞胺磺酸酯Preferably, the sum of w, X and y is at least about 90 or 95 K-mole percent of the total copolymer of the copolymer. In many cases, it is particularly preferable that the polymer contains only the acidic and unstable units and the _ and p-hydroxyl groups, ie, x, v and 7 + in the formula I, and y and z. The sum is equal to 1〇〇〇/0. Similarly, in the formula III, the sum of W, X, y, and 7 is also preferably at least about 60% of the total unit of the copolymer, more preferably about 70 or 80%, and further More preferably, the sum of w, X', y' and Z' is a polymer enthalpy of at least about 90 or 95 mole percent. In many cases, the copolymer of the main enthalpy of the formula Ιπ contains only the acid labile group, the m- and the p-group, and the non-acidic/non-reactive group. Preferably, s is the sum of w, X, 丫, and ζ in the formula m, which is equal to about (10)%. Similarly, in the formulas of formula IIAIV, preferably the sum of wx and y is at least about 6 mole percent of the total polymer unit, more preferably at least about 70 or 80%, and further The sum of w, X and y is at least 9" Ge 95 mole percent of the total polymer unit. In many cases, it is particularly preferred that the polymer contains only the acid labile units and the meta- and para-phenyl units. 'The sum of w and uy in the formulas II and IV is equal to 1%. The polymer of the month can be in the presence of a free radical initiator, in the inert atmosphere 'paper scale, the national standard (CNS) A4袼 (21G x 297 public 91566 -------------------- r order _ "-------- line (please read the back of the note first? Fill in this page again} 1254192 A7 V. Invention Description (I3) (Please read the note on the back and then fill out this page) Surround (such as N2 or argon) and, for example, about 70 or more of it, at a high temperature For example, a free radical polymerization reaction, or a reaction of a plurality of monomers to provide various units as described above; wherein the reaction temperature may vary depending on the reactivity of the particular reagent used and the reaction solvent (eg, The boiling point of the solvent may vary; reference may be made to the exemplary reaction conditions of Example I below. The appropriate reaction temperature for any particular system may be determined empirically by those skilled in the art in light of the present disclosure. Suitable solvents include alcohols such as propanol and butanol; and aromatic solvents such as benzene, benzene, toluene and xylene. Dimethyl sulfoxide and dimethylformamide are also suitable. It can be carried out without using a reaction solvent. The copolymer of the present invention can be prepared using various radical initiators. For example, an azo compound such as azo-bis-2,2,-isobutyronitrile (AIBN) and azo can be used. Bis(cyclohexanecarbonitrile), peroxides, peresters, peracids and persulphates can also be used. Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printing hydroxyl groups (such as m-hydroxystyrene or p-hydroxystyrene) Or other reactive moieties, if necessary, can be condensed into a "masked" form to facilitate the synthesis of the polymer. For example, m-acetate styrene and p-acetic acid styrene can be made separately It is a 'masked' form of meta-hydroxystyrene and p-hydroxystyrene. Other hydroxyl masking agents or protecting groups, such as alkylcarboalkyl groups (forming a decyl ether with a base moiety), such as (CH3)3Si -, (CH3) 2 (butyl) Si-' ((CH3) 3C) 3Si-, etc.; or other alkyl esters such as CH3CH2 (C = 〇 > etc. are also suitable. After the reaction is completed, the test conditions can be used. The masking group is removed. For example, in the presence of a base such as hydrazine, hydrazine or NIOAC, the paper can be heated to form the Chinese National Standard (CNS) A4 specification (10) x 297 public) 13 91566 1254192 A7 B7 V. Description of the invention (Η) polymer. Refer to the exemplary conditions of the examples. (Please read the precautions on the back and then fill out this page.) The monomer can also be directly or "unmasked, in the form of a reaction, for example, by m-hydroxystyrene, p-hydroxystyrene. And a polymerization of a monomer containing a photoacid-labile group such as a third butyl acrylate or a butyl methacrylate. The copolymer of the present invention generally has an average molecular weight (Mw) of from 1,000 to about 10,000. 1〇〇, 〇〇〇, more preferably from about 2, _ to about 3 〇〇〇〇; even more preferably, the molecular weight is about 5, 〇〇〇 or 8,000 to about 25,000 or 30,000; suitable molecular weight distribution (Mw /Mn) is about 3 or less than 3, preferably about 2 or less than 2. The molecular weight (Mw or Mn) of the polymer of the present invention can be determined by the gel permeation color 4. The suitable molecular weight distribution of the copolymer of the present invention comprises about i to 5, more typically from about 3 to 3 or 4. It has been found that the dissolution rate in aqueous tetramethylammonium hydroxide solution decreases as the molecular weight of the copolymer of the present invention increases. As described above, the copolymer of the present invention can be very Useful as a photoresist composition, especially a chemically multiplying positive photoresist The composition component of the present invention comprises a photoactive component and a resin binder component containing the above copolymer. The amount of the resin binder component is sufficient for the photoresist coating. The layer is developed with an aqueous alkaline developer. The photoresist composition of the present invention also includes a photoacid eliminator (ie, "pAG") in an amount sufficient to cause exposure to the photoresist layer upon exposure to active radiation. Potential image. One of the preferred pAGs used in the photoresist of the present invention includes, for example, the lower Thai paper scale applicable to the Chinese National Standard (CNS) A4 specification (21" 297 mm) · 14 91566 1254192 A7 5. Invention Description (U) Imine sulfonate

oso2r 其中R為樟腦、金剛烷 '烷基（如Ci i2烷基）及全氟烷基如全氟（cVu烷基），特別是全氟辛烷磺酸酯、全氟壬烷磺酸醋等之全氟陰離子。特別適合之PAG為N_[(全氟辛烷磺醯基）氧基]-5-去甲萡烯_2,3_二甲醯亞胺。其他磺酸酯化合物如磺酸酯鹽亦可使用。兩種適用劑為下列之PAG 1及2 ·· 2 o3sOso2r wherein R is camphor, adamantane 'alkyl (such as Ci 2 alkyl) and perfluoroalkyl such as perfluoro (cVu alkyl), especially perfluorooctane sulfonate, perfluorodecane sulfonate, etc. Perfluoroanion. A particularly suitable PAG is N_[(perfluorooctanesulfonyl)oxy]-5-nordecene-2,3-dimethylimine. Other sulfonate compounds such as sulfonate salts can also be used. The two suitable agents are the following PAG 1 and 2 ·· 2 o3s

OaSOaS

-------Γ --------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製此磺酸酯化合物可由歐洲專利申請案961181u 2(公告號碼0783 136)揭露内容製備之，該案詳細記載上述pA 1之合成。另外也可將上述二種鎭化合物與除了上述基以外之p 離子絡合。特別是，較佳之陰離子包含具RC〇3_式者，姜中R為金剛烷、烷基（如烷基）及全氟烷基如全氟 i2烧基），特別是全氟辛燒續酸酯、全氟壬燒績酸酯等之木紙張尺度適用中國國家標準（CNS)A4規格（21G x 297公髮） 1254192 五、發明說明（i6 ) 全氟平衡陰離子。其他已知之PAG亦可應用於本發明之光阻劑中。例如，可使用國際申請案W094/10608所敘述之N-磺醯氧亞胺化物’或曝光於活性輻射下會產生鹵酸（如HBr)之非| | 離子性鹵化PAG，後者記述於美國專利案第夂〗28,232號 (Thackeray等人），及歐洲專利申請案第〇164248號及第 0232972 號。本發明光阻組成物較佳之視需要成分為染料化合物。較佳之染料一般藉由降低輻射曝光之反射及其效應（如，刻蝕），而可經顯影之光阻浮雕影像圖案之解析度。較佳之染料包括經取代及未經取代之吩噻畊、吩噚畊、蒽、及蒽三酚化合物。經取代之吩噻哄、吩噚畊、蒽及蒽三酚之較佳取代基包含如㈣子、Ci 12烷基、Ci 12烷氧基、c212 烯基、cN12烷醯基例如乙醯基、芳基例如苯基等。此類線化合物之共聚物亦可當作染料使用’如蒽丙烯酸酯聚合物或共聚物。另較佳之視需要之添加劑為添加驗，特別是氫氧化四丁基銨（TBAH)或TBAH之乳酸鹽，其可加強經顯影之光阻浮雕影像的解析度。其他適用之驗添加劑包含烷基與芳基胺及_。該添加驗使用相當少量即可，如相對= 活性成分（PAG)之約1至20重量％。本發明之光阻劑亦可含有其他視需要之材料，如，包含抗條紋劑、增塑劑、速度加強劑等之其他視需要添加劑。該視需要添加劑一般在光阻組成物中以相當低濃度存在， _本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐Τ' 91566 16 1254192 經濟部智慧財產局員工消費合作社印製 17 A7 B7 五、發明說明（Π ) 惟填充劑及染料可以相當高濃度存在，例如佔光阻劑乾燥成分總重之約5至3 0重量％。本發明之組成物可由熟知此項技術者容易地予以製備。例如’本發明之光阻組成物可由摻合光阻成分至適當溶劑中製備之，該溶劑如乳酸乙酯、乙二醇醚例如2_甲氧***（二乙二醇二甲醚）、乙二醇單甲醚、丙二醇單甲醚 Cellos〇lve(溶纖劑）酯例如甲基乙基酮、及3_乙氧乙基丙酸S旨。一般而言，該組成物之固體含量可於光阻組成物縐重之約5與35重量％間有所不同。樹脂黏合劑與Pag成分之含量應足以提供薄膜塗覆層及形成高品質之潛在及浮雕影像。參考下文實施例2中較佳之光阻成分含量示範。本發明之組成物係根據一般已知之步驟使用。本發明之液體塗覆組成物可藉由如旋轉、浸潰、滾筒塗覆或其他習知之塗覆技術施敷至基板上。於旋轉塗覆時，塗覆溶液之固體含量可以依據所使用之特定旋轉設備、溶液黏度、說轉器速度及谷許旋轉之時間等做適度的調整，以提供所需之薄膜厚度。本發明之光阻組成物可適當地施敷至習知與光阻塗覆相關方法中所用之基板上。例如，該組成物可施敷至矽或二氧化矽晶圓上以製造微處理器及其他積體電路成分。亦可使用鋁-氧化鋁、砷化鎵、陶瓷、石英或鋼基板。用於液晶顯示器及其他平面顯示器之基板亦適用，如玻璃基板、經塗蓋氧化銦錫之基板等。將光阻塗覆於表面後，需加熱移除溶劑直到較好此光本紙張尺度適用中國國家標準（CNS)A4規格m〇 X 297公釐） 91566 -------------------l· -------線 (請先閱讀背面之注音？事項再填寫本頁) A7 1254192 五、發明說明（18 ) 阻塗覆層不剝落為止。其後，經由習知方法透過光罩形成影像。此曝光係足以有效活化光阻系統之光活性成分，以在樹脂塗蓋層上產生圖案影像。詳言之，此曝光能量隨曝光器具及光阻組成物成分而不同，一般介於約1至 300mJ/cm2 之間〇本發明之光阻組成物塗覆層，較佳為以在深紫外線範圍内，亦即少於或等於350nm，或更典型為約少於或等於 300nm範圍内，或典型地約15〇至3〇〇或45〇nm範圍内之曝光波長予以光活化下。特別較佳之曝光波長為約 248nm 〇曝光後，組成物之薄膜層較佳在約7(rc至約15〇。。之溫度下烘烤。之後，將該薄膜顯影。該經曝光之光阻膜藉使用極性顯影劑予以顯影，顯影劑較佳為水性__^ 如無機驗，其例示如氫氧化鈉、氫氧化卸、碳酸納、碳酸氫鈉、矽酸鈉、偏矽酸鈉、氫氧化季銨溶液例如氫氧化四烷銨溶液；各種胺溶液例如乙胺、正丙胺、二乙胺、二正丙胺、三乙胺、或甲基二乙胺；醇胺例如二乙醇胺或三乙醇胺；環胺例如吼n定等。一般情形下，顯影係㈣公$忍已知程序。塗覆於基板上之光阻顯影後，可將該經顯影基板之盈光阻部份予以選擇性加工，例如，依據此項技藝中已知: 程序將無光阻之基板部份做化學触刻或電鍵處理。微電子基板之製造，例如於二氧切晶圓之製造時，適用之蚀刻劑包含^龍刻劑如以氣或氟為基底之蚀刻劑，例如cf M氏張尺度適家標準（CNS)A4規格（2Κ) X 297公釐丁 4 91566 -------- --------線Φ (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 18 1254192 經濟部智慧財產局員工消費合作社印製 19 A7 五、發明說明（l9 ) 或CF^CHF3蝕刻劑，係呈電漿流施用。如上所述，本發明組成物對此等触刻劑具高抗性，因此可應用於製造需交高解析之物件，包含二欠微米之線寬要求。亦可參考下文實施例9之結果。經以上加工後，基板上之光阻可由已知之剝除程序予以移除。本文所有提及之文件内容全部併入本文中以資參考。茲以下列非限制用之實施例說明本發明。實施例1 本發明較佳聚合物之合成（該聚合物含對-經苯乙稀/ 間-經苯乙烯/丙烯酸第三丁酯單元）。於一乾淨乾燥之2頸圓底空燒瓶内，加入1318克 (8.026毫莫耳）AIBN起始劑、7 69克⑼99毫莫耳）丙烯酸第三了醋、45·41克（279.98毫莫耳）間_醋酸基苯乙稀、 9.73克（59·99毫莫耳）對_醋酸基苯乙烯，接著加入14〇毫升2丙醇及26毫升乙腈，使單體中對-羥苯乙烯/間_羥苯乙烯/丙烯酸第三丁醋之莫耳數比為15/7〇/15。以磁棒缓慢攪拌此混合溶液，於溶液表面下方***乂針並抽氣15 至20分鐘。緩慢回流此均相溶液並維持2〇小時。逐滴添加s 52.5克（681.1毫莫耳）醋酸銨之27毫升去離子水溶液至該回流溶液中’產生混濁溶液，繼續回流該溶液，3〇刀鐘後即呈澄清溶液，保持回流過夜。冷卻此黏性聚合物溶液，轉移此溶液至含9〇克（43〇毫克當t_s〇3H)IRN_ 77(已α洗備女）之瓶中，旋轉2小時後過濾該溶液。逐滴添加此聚合物溶液至快速攪拌之去離子水（27〇〇毫升）中， &張尺度適用中國國家標準（CNS)A4規格（g297公釐)---^一 91566 I------------------P 訂--------線· (請先閱讀背面之注意事項再填寫本頁) 1254192 A7 B7 五、發明說明（2〇 ) 則可分離出共聚物。風乾此潮濕糕狀物過夜，並以7 〇真空乾燥20小時，得到46克（94.8%)產物。GPC顯示 Mw=15782, Mn = 8573。Tg=l52t：(第二次加熱為 2〇艽/分鐘），殘留鹼=0.006毫克當量/克。對-羥苯乙烯/間·羥苯乙烯/丙烯酸第三丁酯=1 5/73/12(依據]STMR光譜分析之聚合物各單元莫耳數比）。實處M.2 :光阻製備及微影製程本發明之光阻（以下稱光阻1}係由混合特定量之下列成分而製備：經濟部智慧財產局員工消費合作社印製成分樹脂黏合劑三元共聚物（對-羥苯乙烯/間-羥苯乙烯/丙烯酸第三丁酯 =1 5 / 7 3 /12 ;上述實施例1之共聚物）光活性化合物磺酸二第三丁基苯鏘樟腦磺酸二第三丁基苯鎭驗添加劑乳酸四丁基銨表面活性劑以 Silwet L-7604 甲基矽氧烷溶劑乳酸乙酯販售之聚二含量配製成20重量％ (於溶劑中）相對於樹脂黏合劑為5重量％相對於樹脂黏合劑為0.40重量％ 0.322 克 40.183 克光阻1係經過微影測試。微影程序係使用丨5〇毫米』本紙張尺度適用中家標準（CNS)A4規格⑽x 297公愛） 20 91566 1®^-------^-訂--------線 (請先閱讀背面之注意事項再填寫本頁) 1254192 A7 五、發明說明（21 (請先閱讀背面之注意事項再填寫本頁) 20〇毫米兩種石夕晶圓於現代晶圓加工器具（由FSI及svG 么司製造）上進行。所有加工處理係在主要不含鹼性污染物之氛圍（<5ppb測量之胺/氨）進行。於後續加工之前，晶圓表面塗覆有機ARC組成物。於約3000rpm轉速下，將光阻以旋轉方式塗覆於晶圓上，並於130 °C在接近150# m間隙之墊板上烘烤60秒（PAB，處理後烘烤），然後快速冷卻至室溫。將此薄膜使用解析度測試圖案，於DUV步進機（248nm)上進行曝光。曝光後立刻於i3(rc將薄膜置接近150 // m間隙之墊板上烘烤9〇秒（pEB，曝光後烘烤），接著快速冷卻至室溫。然後立刻將此薄膜以〇 26N氫氧化四甲基叙顯影劑用45秒執跡單一混伴法（traek-single-puddle process)予以顯影。藉由掃描式電子顯微鏡分析結果顯示，獲得高解析度光阻浮雕影像。實施例3至11 經濟部智慧財產局員工消費合作社印製以實施例1所述之相同程序，合成下列九個另外之聚合物。該共聚物之組成及其他特性列於下面表1中。實施例3至11之共聚物僅由對-羥苯乙烯（pHS)、間-羥苯乙烯 (mHS)及丙烯酸第三丁酯（tBA)之聚合單元組成，其莫分百分率係由表1所列之各單元的C13-NMR予以測定。本紙張尺度綱巾關賴準（CNS)A4規格（210 X 297公釐） 21 91566 A7 1254192 _______B7_ 五、發明說明（22 ) 表1 之共聚物 pHS mHS tBA Mw Tg(°C 3 10 70 20 9937 143 4 15 65 20 10068 145 5 31 53 16 26417 157 6 12 71 17 16037 149 7 11 74 15 25429 151 8 15 73 12 1 5785 152 9 21 71 8 16340 154 10 11 81 8 26827 153 11 21 63 16 25575 152 上述共聚物塗覆層於水性氫氧化四甲基銨溶液中之溶解速率隨該共聚物分子量之增加而降低。該溶解速率亦隨共聚物之mHS單元莫耳量增加而降低。上文之陳述僅係本發明之說明，故須知在不脫離本發明下揭請求專利範圍之精神與範疇下，可進行各種改變及修飾。 ----------I -------P 訂— ^--------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 22 91566-------Γ -------- Line (please read the note on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Print this sulfonate compound from European patent application 961181u 2 (Announcement No. 0783 136) discloses the preparation of the content, and the case details the synthesis of the above pA 1 . Alternatively, the above two hydrazine compounds may be complexed with p ions other than the above groups. In particular, preferred anions comprise those having the formula RC〇3_, wherein R is adamantane, alkyl (such as alkyl) and perfluoroalkyl such as perfluoroalkyl i2), especially perfluorooctanoic acid Wood paper scales such as esters, perfluoroantimony-based acid esters, etc. are applicable to China National Standard (CNS) A4 specification (21G x 297 mil). 1254192 V. Description of invention (i6) Perfluoro equilibrium anion. Other known PAGs can also be used in the photoresist of the present invention. For example, the N-sulfonyloxyimide described in International Application No. W094/10608 or the non-|ionically halogenated PAG which is exposed to active radiation to produce a halogen acid such as HBr, which is described in the U.S. patent, may be used. Case No. 28,232 (Thackeray et al.), and European Patent Application Nos. 164248 and No. 0232972. Preferably, the photoresist composition of the present invention is a dye compound as desired. Preferred dyes typically have a resolution of the developed photoresist image by reducing the reflection of the radiation exposure and its effects (e.g., etching). Preferred dyes include substituted and unsubstituted thiophene, arsenic, hydrazine, and ninhydrin compounds. Preferred substituents of substituted phenothiazine, phenanthrene, anthraquinone and quinolol include, for example, (tetra), Ci 12 alkyl, Ci 12 alkoxy, c212 alkenyl, cN12 alkyl fluorenyl, e.g. An aryl group such as a phenyl group or the like. Copolymers of such linear compounds can also be used as dyes such as oxime acrylate polymers or copolymers. A further preferred additive is an additive test, particularly tetrabutylammonium hydroxide (TBAH) or TBAH lactate, which enhances the resolution of the developed photoresist image. Other suitable test additives include alkyl and arylamines and _. The addition test can be used in a relatively small amount, such as from about 1 to 20% by weight of the active ingredient (PAG). The photoresist of the present invention may also contain other materials as desired, such as other optional additives including anti-striation agents, plasticizers, speed enhancers, and the like. The additive as needed generally exists in a relatively low concentration in the photoresist composition. _ This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 cm Τ ' 91566 16 1254192 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative Process 17 A7 B7 V. INSTRUCTIONS (Π) However, fillers and dyes may be present in relatively high concentrations, for example from about 5 to about 30% by weight based on the total weight of the dry component of the photoresist. The compositions of the present invention may be well known in the art. It can be easily prepared. For example, the photoresist composition of the present invention can be prepared by blending a photoresist component into a suitable solvent such as ethyl lactate, glycol ether such as 2-methoxyethyl ether (diethylene glycol). Dimethyl ether), ethylene glycol monomethyl ether, propylene glycol monomethyl ether Cellos〇lve (cellosolve) esters such as methyl ethyl ketone, and 3-ethoxyethyl propionic acid S. In general, the composition The solids content of the material may vary between about 5 and 35% by weight of the photoresist composition. The amount of resin binder and Pag component should be sufficient to provide a film coating and to form a high quality potential and relief image. Below The preferred composition of the photoresist component in Example 2 is demonstrated. The composition of the present invention is used according to generally known procedures. The liquid coating composition of the present invention can be applied by, for example, spinning, dipping, roller coating or other conventional coatings. The coating technique is applied to the substrate. During spin coating, the solid content of the coating solution can be adjusted according to the specific rotating equipment used, the viscosity of the solution, the speed of the converter, and the time of rotation of the valley to provide The desired film thickness. The photoresist composition of the present invention can be suitably applied to a substrate used in a conventional method related to photoresist coating. For example, the composition can be applied to a tantalum or niobium dioxide wafer. It is used to manufacture microprocessors and other integrated circuit components. Aluminum-aluminum oxide, gallium arsenide, ceramic, quartz or steel substrates can also be used. Substrates for liquid crystal displays and other flat panel displays, such as glass substrates, Coating the substrate of indium tin oxide, etc. After applying the photoresist to the surface, it is necessary to heat and remove the solvent until the standard of this paper is suitable for the Chinese National Standard (CNS) A4 specification m〇X 297 mm) 91566 -------------------l· ------- line (please read the phonetic on the back? Please fill out this page again) A7 1254192 V. Description of invention (18) The coating layer is not peeled off. Thereafter, an image is formed through the reticle by a conventional method. This exposure is sufficient to effectively activate the photoactive component of the photoresist system to produce a patterned image on the resin coating. In detail, the exposure energy varies depending on the exposure device and the composition of the photoresist composition, and is generally between about 1 and 300 mJ/cm 2 . The photoresist composition coating layer of the present invention is preferably in the deep ultraviolet range. Exposure wavelengths within the range of less than or equal to 350 nm, or more typically less than or equal to 300 nm, or typically from about 15 Å to 3 Å or 45 Å are photoactivated. A particularly preferred exposure wavelength is about 248 nm. After exposure, the film layer of the composition is preferably baked at a temperature of from about 7 (rc to about 15 Å). Thereafter, the film is developed. The exposed photoresist film By developing with a polar developer, the developer is preferably aqueous __^ such as an inorganic test, which is exemplified by sodium hydroxide, hydroxide dehydration, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, and hydroxide. a quaternary ammonium solution such as a tetraammonium hydroxide solution; various amine solutions such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, or methyldiethylamine; an alcoholamine such as diethanolamine or triethanolamine; The amine is, for example, 吼n. In general, the developing system (4) is known to have a known procedure. After the photoresist is applied to the substrate, the photoresist portion of the developed substrate can be selectively processed, for example, According to the art, it is known that: the program performs chemical touch or key treatment on the substrate portion without photoresist. The manufacture of the microelectronic substrate, for example, in the manufacture of a dioxy-cut wafer, the applicable etchant comprises An engraving agent such as a gas or fluorine based etchant, Such as cf M's Zhang Scale Standard (CNS) A4 specification (2Κ) X 297 cm D 4 91566 -------- -------- Line Φ (Please read the back note first) ? Matters to fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed 18 1254192 Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed 19 A7 V, invention description (l9) or CF ^ CHF3 etchant, is a plasma flow Application As described above, the composition of the present invention is highly resistant to such etchants, and thus can be applied to the manufacture of articles requiring high resolution, including line width requirements of two micrometers. See also Example 9 below. As a result, after the above processing, the photoresist on the substrate can be removed by a known stripping procedure. The contents of all the documents mentioned herein are hereby incorporated by reference in their entirety for all of the the the the EXAMPLE 1 Synthesis of a preferred polymer of the invention (the polymer comprises p- styrene/m-styrene/t-butyl acrylate unit) in a clean, dry 2-neck round bottom flask , adding 1318 g (8.026 mmol) AIBN starter, 7 69 g (9) 99 mmoles) Acrylic third vinegar, 45.41 grams (279.98 millimoles) _acetic acid styrene, 9.73 grams (59.99 millimoles) of _acetic acid styrene, followed by 14 liters of 2 propanol and 26 ml of acetonitrile gave a molar ratio of p-hydroxystyrene/m-hydroxystyrene/acrylic acid terpene vinegar of 15/7 〇/15. The mixture was slowly stirred with a magnetic bar, and the needle was inserted under the surface of the solution and pumped for 15 to 20 minutes. This homogeneous solution was slowly refluxed and maintained for 2 hours. s 52.5 g (681.1 mmol) of ammonium acetate in 27 ml of deionized water was added dropwise to the refluxing solution to produce a turbid solution. The solution was refluxed and a clear solution was obtained after 3 knives and kept at reflux overnight. The viscous polymer solution was cooled, and the solution was transferred to a bottle containing 9 gram (43 〇 mg when t_s 〇 3H) IRN_ 77 (α-washed female), and the solution was filtered after being rotated for 2 hours. Add this polymer solution dropwise to the rapidly stirred deionized water (27 〇〇ml), & Zhang scale is applicable to China National Standard (CNS) A4 specification (g297 mm)---^91566 I--- ---------------P Order -------- Line · (Please read the back note and then fill out this page) 1254192 A7 B7 V. Invention Description (2〇 ) The copolymer can be isolated. The moist cake was air dried overnight and dried under vacuum for 7 hours to give 46 g (94.8%) of product. GPC shows Mw = 15782, Mn = 8573. Tg = l52t: (second heating was 2 Torr/min), residual alkali = 0.006 meq/g. p-Hydroxystyrene/m-hydroxystyrene/tributyl acrylate = 15/73/12 (molar ratio of each unit of polymer according to STMR spectroscopy). Practice M.2: Photoresist preparation and lithography process The photoresist of the present invention (hereinafter referred to as photoresist 1) is prepared by mixing a specific amount of the following components: Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed with resin adhesive 3 Meta-copolymer (p-hydroxystyrene/m-hydroxystyrene/third butyl acrylate = 15 / 7 3 /12; copolymer of the above Example 1) photoactive compound di-tert-butylphenyl sulfonate Camphorsulfonic acid di-tert-butylphthalide test additive tetrabutylammonium lactate surfactant is prepared in a solvent content of 20% by weight of the polydiethylene content sold by Silwet L-7604 methyloxane solvent ethyl lactate (in solvent) ) 5% by weight relative to the resin binder 0.40% by weight relative to the resin binder 0.322 gram 40.183 gram of the photoresist 1 is subjected to lithography. The lithography procedure is 丨 5 〇 mm. This paper size is suitable for the Chinese standard ( CNS) A4 size (10) x 297 public) 20 91566 1®^-------^-book-------- line (please read the notes on the back and fill out this page) 1254192 A7 V. Description of the invention (21 (please read the precautions on the back and fill out this page) 20 mm two stones The wafers are processed on modern wafer processing equipment (manufactured by FSI and svG). All processing is carried out in an atmosphere that is mainly free of alkaline contaminants (<5ppb measured amine/ammonia). Previously, the surface of the wafer was coated with an organic ARC composition. The photoresist was applied to the wafer in a rotational manner at about 3000 rpm and baked at 130 ° C for 60 seconds on a pad close to the 150 # m gap. (PAB, post-treatment bake), then rapidly cooled to room temperature. The film was exposed to a DUV stepper (248 nm) using a resolution test pattern. Immediately after exposure, i3 (rc placed the film close to 150 / Baking on the pad of /m gap for 9 sec (pEB, post-exposure bake), then rapidly cooling to room temperature. Then immediately apply this film as 〇26N tetramethyl hydride developer for 45 seconds. The traek-single-puddle process was developed. The results of scanning electron microscopy showed that high-resolution photoresist embossed images were obtained. Examples 3 to 11 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed to implement The same procedure as described in Example 1. The following nine additional polymers were synthesized. The composition and other properties of the copolymer are listed in Table 1. The copolymers of Examples 3 to 11 were only composed of p-hydroxystyrene (pHS), m-hydroxystyrene (mHS). And the composition of the polymerized unit of tert-butyl acrylate (tBA), the molar percentage of which is determined by C13-NMR of each unit listed in Table 1. The paper scale is based on the CNS A4 specification (210) X 297 mm) 21 91566 A7 1254192 _______B7_ V. INSTRUCTIONS (22) The copolymer of Table 1 pHS mHS tBA Mw Tg (°C 3 10 70 20 9937 143 4 15 65 20 10068 145 5 31 53 16 26417 157 6 12 71 17 16037 149 7 11 74 15 25429 151 8 15 73 12 1 5785 152 9 21 71 8 16340 154 10 11 81 8 26827 153 11 21 63 16 25575 152 The above copolymer coating layer in aqueous tetramethylammonium hydroxide solution The rate of dissolution in the polymer decreases as the molecular weight of the copolymer increases. The rate of dissolution also decreases as the amount of mHS units in the copolymer increases. The above description is only illustrative of the invention, and it is to be understood that various changes and modifications may be made without departing from the spirit and scope of the invention. ----------I -------P Order - ^-------- line (please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Office staff The consumer cooperative printed this paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 22 91566

Claims

9,1254192 H3 邮3琢5^^!^申請案範圍修正本 ,__ r (93 年 3 月 26 曰） \種光阻組成物，係包括光活性成分及含有聚合物之 f月曰’錢合物包括⑴酸式不穩定基、⑵間—經苯土及(3)對-羥苯基’其中該聚合物包括下式η之結構··9,1254192 H3 Post 3琢5^^!^Revised scope of the application, __ r (March 26, pp. 93) \A kind of photoresist composition, including photoactive ingredients and polymers containing polymer The composition includes (1) an acid labile group, (2) a benzoic acid, and (3) a p-hydroxyphenyl group, wherein the polymer includes a structure of the following formula:

R4 W X Η0 〜V)m l'(R2)n II 基；其中R為視需要經取代之炫基； R〗及R2各自為相同或不同之非_氳取代基； R、R及R5各自分別為氫或視需要經取代之烷經濟部中央標準局員工福利委員會印製 m及η各自分別為〇至4 ;以及 w、x及y各自大於〇,且為該聚合物各別單元之莫耳百分率。 2.如申請專利範圍第丨項之光阻組成物，其中w、X及 y之總和為該聚合物總單元之至少約9〇莫耳百分率。 3 · —種光阻組成物，係包括光活性成分及含有聚合物之樹脂，該聚合物包括（1)酸式不穩定基、（2)間—經苯本紙張尺度適家標f(CNS) A4規格（210__χ 297公髮 1254192 =(3)對—經苯基’其中該聚合物包括下式ιπ之結R4 WX Η0 〜V)m l'(R2)n II group; wherein R is a thiol group which is optionally substituted; R and R2 are each the same or different non-氲 substituent; R, R and R5 are respectively For the hydrogen or as needed, the Alkali Ministry of Economics, the Central Bureau of Standards, the Staff Welfare Committee, prints m and η, respectively, to 44; and w, x and y are each greater than 〇, and is the individual unit of the polymer. percentage. 2. The photoresist composition of claim 3, wherein the sum of w, X and y is at least about 9 mole percent of the total polymer unit. 3 · A photoresist composition comprising a photoactive component and a polymer-containing resin, the polymer comprising (1) an acid labile group, (2) a medium-sized paper-based standard f (CNS) A4 size (210__χ 297 mils 1254192 = (3) pairs - by phenyl 'where the polymer includes the knot of the following formula

III 其中W包括酸式不穩定基； R及R2各自為相同或不同之非-氫取代基；以3、1^、1^、及116各自分別為氫或視需要經取代之烷基； m及η各自分別為〇至4 ;以及 S為不含酸性或酸性反應性部份之基； w、X’、y’及Ζ’各自大於0，且為該聚合物各別單元之莫耳百分率。 4.如申睛專利範圍第3項之光阻組成物，其中w，、X，、 y及z ’之總和為該聚合物總單元之至少約9 〇莫耳百分率。經濟部中央標準局員工福利娄員會印製 5 · —種光阻組成物，係包括光活性成分及含有聚合物之樹脂’該聚合物包括（1 )酸式不穩定基、（2 )間-羥苯基及（3)對-羥苯基，其中該聚合物包括下式IV之結構：本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公釐） 91 1254192 ^一^~~~__ H3III wherein W includes an acid labile group; R and R2 are each the same or different non-hydrogen substituent; each of 3, 1^, 1^, and 116 is hydrogen or optionally substituted alkyl; And η are each 〇 to 4; and S is a group which does not contain an acidic or acidic reactive moiety; w, X', y' and Ζ' are each greater than 0 and is the percentage of moles of the individual units of the polymer . 4. The photoresist composition of claim 3, wherein the sum of w, X, y and z' is at least about 9 〇 mole percent of the total polymer unit. The Central Bureau of Standards and Staff of the Ministry of Economic Affairs will print 5 kinds of photoresist components, including photoactive components and polymers containing polymers. The polymer includes (1) acid-labile groups, and (2) -Hydroxyphenyl and (3) p-hydroxyphenyl, wherein the polymer comprises the structure of the following formula IV: The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 91 1254192 ^一^~ ~~__ H3

/、ι中R為視需要經取代之烷基； R及R3各自分別為氫或甲基； \γ Λ X /- y各自大於〇，且為該聚合物各別單之莫耳百分率。 6.如申請專利範圍第5項之光阻組成物，其中r為第三丁基至剛烷基、四氫吡喃基、或去曱萡烷基。 7·如申請專利範圍第5項之光阻組成物，其中w、χ及 y之4和為该聚合物總單元之至少約90莫耳百分率。 8· —種形成光阻浮雕影像（reHefimage)之方法，係包括： (a) 塗覆一層如申請專利範圍第1、3或5項之光阻組成物至基板上；以及經濟部中央標準局員工福利委員會印製 (b) 將該基板上之該光阻塗層曝光及顯影，以產生光阻浮雕影像。 9.如申請專利範圍第8項之方法，其中該基板為微電子晶圓或平面顯示器基板。 1 〇·如申請專利範圍第1、3或5項之光阻組成物，其係塗覆於製造物件之基板上。本張尺i適用格⑽公 3 町卿r^r 1254192 之組成物-，板電子s曰®或平面顯示器基板。 12·一種用於光阻之聚合物，其係包括： (i)l式不穩定基；（2)間-羥苯基；及（3)對-羥笨基，其中該聚合物包括下式IV所示之結構：R, R is an optionally substituted alkyl group; R and R3 are each hydrogen or methyl; \γ Λ X / - y are each greater than 〇, and are the molar percentages of the polymer. 6. The photoresist composition of claim 5, wherein r is a third butyl to a nonylalkyl group, a tetrahydropyranyl group, or a dedecylalkyl group. 7. A photoresist composition according to claim 5, wherein 4 of w, χ and y is at least about 90 mole percent of the total polymer unit. 8. A method of forming a resist image (reHefimage) comprising: (a) coating a layer of a photoresist composition as disclosed in claim 1, 3 or 5 onto a substrate; and the Central Bureau of Standards of the Ministry of Economy The employee welfare committee prints (b) exposing and developing the photoresist coating on the substrate to produce a photoresist relief image. 9. The method of claim 8, wherein the substrate is a microelectronic wafer or a flat display substrate. 1 〇 A photoresist composition as claimed in claim 1, 3 or 5, which is applied to a substrate on which the article is manufactured. This ruler i is suitable for the composition of the grid (10) Gong 3 machiqing r^r 1254192 - board electronic s曰® or flat panel display. 12. A polymer for photoresist comprising: (i) an unstable group of formula (1), (2) an m-hydroxyphenyl group; and (3) a p-hydroxyphenyl group, wherein the polymer comprises the following formula Structure shown in IV:

IV 其中R為視需要經取代之烷基； Rl、R2’及R3’各自分別為氫或甲基； W、X、及y各自大於〇，且為該聚合物各別單元之莫耳百分率。經濟部中央標準局員工福利委員會印製 I釐 I公 97 2 X 10 2 /(\ 格 i規 A4 I ) S N C /(V 準標 |家國國 I中一用一適一度尺一張一紙 !本一 i 正修 )uv -Wherein R is an optionally substituted alkyl group; R1, R2' and R3' are each hydrogen or methyl; W, X, and y are each greater than 〇, and are the percentage of moles of the individual units of the polymer. Ministry of Economic Affairs, Central Bureau of Standards, Staff Welfare Committee, Printing I I, I. 97 2 X 10 2 / (\ 格 i regulation A4 I) SNC / (V standard | Home country I in one with a suitable ruler and a piece of paper !本一i 正修)uv -